WO1999033894A1 - Silicone-containing prepolymers and low water materials - Google Patents

Silicone-containing prepolymers and low water materials

Info

Publication number
WO1999033894A1
WO1999033894A1 PCT/US1998/026186 US9826186W WO9933894A1 WO 1999033894 A1 WO1999033894 A1 WO 1999033894A1 US 9826186 W US9826186 W US 9826186W WO 9933894 A1 WO9933894 A1 WO 9933894A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
monomer
elastomer
amino
prepolymer
thermoplastic
Prior art date
Application number
PCT/US1998/026186
Other languages
French (fr)
Inventor
Paul L. Valint, Jr.
Yu-Chin Lai
Edmond T. Quinn
Daniel M. Ammon, Jr.
Original Assignee
Bausch & Lomb Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made
    • G02B1/04Optical elements characterised by the material of which they are made made of organic materials, e.g. plastics
    • G02B1/041Lenses
    • G02B1/043Contact lenses
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/61Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/64Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6469Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having silicon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Abstract

Low water silicone-containing elastomers are based on a hydroxy- or amino-terminated prepolymer derived from an ethylenically unsaturated silicon-containing monomer, and at least one monomer reactive with hydroxyl- or amino-functional radicals of the prepolymer. The elastomers are especially useful as contact lens materials.

Description

SILICONE-CONTAINING PROPOLYMERS AND LOW WATER MATERIALS

BACKGROUND OF THE INVENTION

The present invention generally relates to silicone-containing materials useful as a contact lens material.

Polymeric silicone materials for contact lens applications include hydrogels and non-hydrogels. The non-hydrogels may include rigid materials, useful for rigid gas permeable contact lenses, or flexible materials useful for soft contact lenses. Whereas hydrogels typically include appreciable amounts of hydrophilic monomers and/or internal wetting agents and absorb and retain appreciable amounts of water, the non- hydrogel silicone materials do not include appreciable amounts of such hydrophilic monomers or wetting agents. Therefore, these "low water" non-hydrogel silicone materials do not absorb or retain appreciable amounts of water, for example, less than about 5 weight percent, and more typically less than about 1 or 2 weight percent.

It is important that low water silicone compositions, especially for soft contact lens applications, have desirable oxygen permeability, modulus and elastic recovery characteristics. This is particularly important in the formation of soft contact lenses, as the modulus (Young's modulus of elasticity) and elastic recovery of the lens material can have a significant impact upon lens "comfort." Lenses possessing high modulus often have a perceived stiffness; lenses with too high elastic recovery can exhibit a "suction cup" effect on the eye.

One class of silicone monomers commonly used in silicone-containing contact lens materials are bulky polysiloxanylalkyl methacrylates, e.g. methacryloxypropyl tris (trimethylsiloxy) silane (commonly referred to as "TRIS"). Since these "bulky" monomers contain a large amount of silicon per molecule, they are useful for increasing oxygen permeability of materials, a desirable property for contact lens and other biomedical device applications. However, although TRIS is known to reduce the modulus of some silicone hydrogels, i.e., polyurethane-polysiloxane hydrogel compositions, (see for example; Lai, Yu Chin, The Role of Bulky Polvsiloxanylalkyl Methacrylates in Polyureihane-polvsiloxane Hydrogels, Proceedings of the American Chemical Society Division of Polymeric Materials: Science and Engineering, Vol. 72, pg. 118-1 19, (1995)), the use of TRIS monomeric units within "low water" silicone compositions generally increases the modulus of the resulting material. As such, TRIS monomeric units are not generally helpful in reducing the modulus of low water silicone materials.

Another class of silicone monomers known for silicone-containing contact lens materials are elastomers based on ethylenically endcapped polydimethylsiloxanes, such as the polydimethylsiloxanes disclosed in US Patent No. 4, 153,641. These materials usually provide elastomers with relatively low modulus.

In summary, low water silicone materials are sought for soft contact lens applications which possess relatively low modulus, for example from 20 g/mm2 to about 150 g/mm2, and with a suitable elastic recovery rate. Furthermore, for such applications, the materials must be optically clear, manufacturable (e.g., capable of being molded or machined), have acceptable oxygen permeability, biocompat.ibility and resist deposit formation. Moreover, low water materials are desired that can be cast into articles such as contact lenses by methods other than free radical polymerization, for example, by injection molding.

SUMMARY OF THE INVENTION

The present invention relates to a silicone composition, preferably a low water silicone composition, which is the polymerization product of a mixture comprising:

(A) a hydroxy- oi amino-terminated prepolymer prepared by reacting the following components:

(a) 60 to 95 mole % of an ethylenically unsaturated silicon-containing monomer,

(b) 2.5 to 20 mole % of an ethylenically unsaturated monomer containing a hydroxyl or amino radical, (c) 2.5 to 20 mole % of a chain transfer agent that provides the prepolymer with hydroxyl- or amino- functional radicals, and

(d) 0 to 20 mole % of an ethylenically unsaturated monomer other than monomers (a), (b) or (c), the mole percent of components (a), (b), (c) and (d) being based on the total mclar amount of said components; and

(B) at least one monomer reactive with hydroxyl- or amino-functional radicals of the prepolymer.

The invention further relates to contact lenses formed on the above-described silicone-containing composition.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The hydroxy- or amino-terminated prepolymer derived from ethylenically unsaturated monomers can be synthesized by general techniques known in the art. Generally, these prepolymers are prepared by free radical polymerization of a mixture of the ethylenically unsaturated silicon-containing monomer (a), the ethylenically unsaturated monomer containing a hydroxyl or amino radical (b) and the ethylenically unsaturated monomer (d) (if present), in the presence of the chain transfer agent (c). The chain transfer agent is selected such that the resultant prepolymer has hydroxy- or amino- terminal functional radicals.

Accordingly, the hydroxy- or amino-terminated prepolymer is derived from an ethylenically unsaturated silicone-containing monomer (a). It is noted that since this silicone-containing monomer is included in at least 60 molar percent of the prepolymer, the prepolymer contains a relatively high amount of silicone per molecule which is important in providing the prepolymer with relatively high oxygen permeability is derived from the silicone-containing monomer (a) is preferably included. This precursor to the hydroxy- or amino-terminated prepolymer may include ethylenically unsaturated silicone- containing monomers known in the contact iens art, and it is preferred that this monomer is monofunctional, i.e., including only one ethylenically unsaturated radical. Most preferred are known bulky polysiloxanylalkyl (meth)acrylic monomers represented by Formula (II):

wherein:

X denotes -COO-, -CONR4-, -OCOO-, or -OCONR4- where each R4 is independently hydrogen or lower alkyl; R3 denotes hydrogen or methyl; h is 1 to 10; and each R2 independently denotes a lower alkyl radical, a phenyl radical or a radical of the formula

-Si(R5)3 wherein each R5 is independently a lower alkyl radical or a phenyl radical.

Such bulky monomers specifically include pentamethyldisiioxanyl methylmethacrylate, tris(trimethylsiloxy) methacryloxy propylsilane, phenyltetramethyl- disiloxanylethyl acrylatε, methyldi(trimethylsiloxy)mεthacryloxymethyl silane, 3- [tιis(trimethylsiloxy)silyl] propyl vinyl carbamate, 3-[tris(trimεthylsiloxy)silyl] propyl allyl carbamate, and 3-[tris(trirnethylsiloxy)silyl] propyl vinyl carbonate.

The hydroxy- or amino-terminated prepolymer is also derived from the ethylenically unsaturated monomer containing a hydroxyl or amino radical (b). Hydroxy- substituted monomers include hydroxy (meth)acrylates and (meth)acryiamides, such as 2- hydroxyethyl methacrylate, 2-hydroxyεthyl acrylate, glycεrcl mεthacrylatε, glycεro! acrylate, and N-2-hydroxyethyl methacrylamide. Amino-substitutcd monomers include allyl amine. Since the described preferred monomers are typically hydrophilic, it is preferred that the hydroxy- or amino-terminatεd prεpolymer includes no more than 20 molar percent of this monomer so that the resultant prepolymer does not absorb or retain appreciable amounts of water. Monomer (b) provides a functional radical (hydroxy or amino) that is reactive with the chain transfer agent (c).

The hydroxy- or amino-terminated prepolymer may optionally include other monomeric units, i.e., this prepolymer may optionally be derived from ethylenically unsaturated monomer (d) that is distinct from monomers (a) and (b). Generally, this prepolymer precursor will be a non-hydrophilic monomer so that the resultant prepolymer is hydrophobic. Examples are hydrophobic (meth)acrylic esters, such as alkyl (meth)acrylates and fluoroalkyl (meth)acrylates wherein the alkyl moiety contains 1-5 carbon atoms.

The chain transfer agent (c) serves to control the molecular weight of the prepolymer and provides hydroxy- or amino- functionality to the prepolymer, so that the prepolymer can be copolymerized with other monomers reactive with the hydroxy- or amino-functionality. Suitable chain transfer agents include mercapto alcohols (also referred to as hydroxymercaptans) and aminomercaptans Prefεrrεd chain transfer agents include 2-mercaptoethanol and 2-aminoethanεthiol. Generally, the molar ratio of chain transfer agent to monomεrs (a), (b) and (d) will bε about 0.01 to about 0.2.

Thε chain transfer agent (c) is also selected so that it is reactive with the hydroxyl or amino radicals of monomer (b) For examplε, when monomer (b) contains a hydroxyl radical (from a monomer such as 2-hydroxyethyl methacrylate), suitable chain transfer agents are those that include a radical reactive with the hydroxyl radical, such as 2- mercaptoethanol. When monomer (b) contains an amino radical (from a monomer such as allylamine), suitable chain transfer agents are those reactive with the amino radical, such as 2-aminoethanethiol. Generally, the chain transfer agent will be included at a molar ratio of 1 : 1 based on the ethylenically unsaturated monomer (b).

Further examples of hydroxy- or amino-terminated prepolymεrs are providεd in the Examples.

The resultant hydroxy- or amino-terminated prepolymer is copolymerized with at least one other comonomer that is reactive with hydroxyl- or amino-functional radicals of the prepolymer to form a thermoplastic elastomer. As used herεin, the term "monomer" or "comonomer" denotes monomeric materials that are copolymerizable with the above- described hydroxy- or amino-terminated prepolymer. Thus, these terms include relatively low molecular weight monomeric materials, and relatively high molecular weight monomeric materials also referred to in the art as prepolymers or macromonomers.

Preferably, the hydroxy- or amino-terminated prepolymers are included at about 10 to about 90 weight percent of the monomer mixture (the total weight percent of the monomer mixture being based on weight of the monomeric components), more preferably at about 25 to about 75 weight percent.

One preferred class of comonomers are silicone-containing monomers which will further increase silicone content, along with oxygen permeability, of the resultant elastomer. One suitable class of comonomers are polysiloxane-containing monomers endcapped with hydroxy or amino radicals, represented by Formula (III):

R' R

I I

X-R— Si — (0— Si)— R-X (DT)

R R wherein each X is hydroxy or amino radical; each R is independently selected from an alkylene group having 1 to 10 carbon atoms wherein the carbon atoms may include ether, urethane or ureido linkages there between; each R' is independently selected from monovalent hydrocarbon radicals or halogεn substitutεd monovalεnt hydrocarbon radicals having 1 to 18 carbon atoms which may include ether linkages there between, and a is an integer equal to or greater than 1. Preferably, each R' is independently selected from alkyl groups, phenyl groups and fluoro- substituted alkyl groups, and each R is alkylene, preferably butylene. Prefεrably, a is about 10 to about 100, more preferably about 15 to about 60.

Another preferred class of comonomers are diisocyanates that react with hydroxy- or amino-functionality of the prepolymers (and with hydroxy- or amino-functionality of the silicone-containing monomers of Formula (III)) to form a polyurethane block elastomer (in the case of prepolymers of Formula (I) including hydroxyl-functionality) or polyurea elastomers (in the case of prepolymers of Formula (I) including amino- functionality). Methods for forming thermoplastic urethane or urea copolymers are known in the art, and a representative synthesis is described in the Examples. Generally, any diisocyanate may be employed; these diisocyanates may be aliphatic or aromatic, and include alkyl, alkyl cycloalkyl, cycloalkyl, alkyl aromatic and aromatic diisocyanates preferably having 6 to 30 carbon atoms in the aliphatic or aromatic moiety. Specific examples include isophorone diisocyanate, hexamethylene-1,6- diisocyanate, 4,4'- dicyclohexylmethane diisocyanate, toluene diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'- diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,4-phenylene 4,4'-diphenyi diisocyanate, l,3-bis-(4,4'-isocyanto methyl) cyclohexane, and cyclohexane diisocyanate. Other examples are diisocyanates which are the reaction product of a diisocyante and a short-chain diol at a 2: 1 molar ratio.

It is preferred to further include as a comonomer a relatively low molecular weight diol or and glycol. These include an alkyl diol, a cycloalkyl diol, an alkyl cycloalkyl diol, an aryl diol or an alkylaryl diol having 1 to 40 carbon atoms and which may contain ether, thio or amine linkages in the main chain. Such materials are useful as chain extenders of the polyurethane or polyurea elastomer. Specific examples include 2,2-(4,4'- dihydroxydiphenyl)propane (bisphenol-A), 4.4'-iso-propylidine dicyclohexanol, ethoxylated and propoxylated bisphenol-A, 2,2-(4,4'-dihydroxydiphenyl)pentane, 1, 1 '- (4,4'-dihydroxydiphenyl)-p-diisopropyl benzene, 1,3-cyclohexane diol, 1,4-cyclohexanε diol, 1-4-cyclohexane dimethanol, neopentyl glycol, 1.4-butanediol, 1,3-propanediol, 1,5- pentanediol, diethylene glycol and triethylene glycol. Especially preferred are alkyl and oxyalkylene diols having 1 to 10 carbon atoms.

Accordingly, a preferred class of elastomers are the polymerization product of a mixture comprising:

(A) the hydroxy- or amino-terminated prepolymer;

(B 1) the silicone containing monomer endcapped with hydroxy or amino radicals, preferably a polysiloxane of Formula (III),

(B2) a diisocyanate, preferably having 6 to 30 carbon atoms in the aliphatic or aromatic moiety; (B3) and a diol or glycol, preferably an alkylene or oxyalkylene diol having 1 to 10 carbon atoms.

The molar ratio of prepolymer (A) to comonomers (Bi), (B2) and (B3) is preferably within the range of 3 : 1 to 1:3, most preferably about 1: 1.

The monomer mix of the present invention may include additional constituents such as colorants or UN-absorbing agents known in the contact lens art.

The monomer mixes can be cast into shaped articles, such as contact lenses, by. methods such as injection or compression molding. More specifically, the monomeric mixture including the hydroxy- or amino-terminated prepolymer and comonomers are charged to a mold cavity having the desired shape of a contact lens and then cured to form a thermoplastic elastomer, with the addition of heat to facilitate curing if desired. The mold may be formed of two mold sections, one mold section shaped to form the anterior lens surface and the other mold section shaped to form the posterior lens surface, and may be either plastic or metal. One advantage of the materials of the invention is that they are suitable for injection molding.

When used in the formation of contact lenses, it is preferred that the subject thermoplastic elastomers have water contents of less than about 5 weight percent and more preferably less than about 1 weight percent. Furthermore, it is preferred that such elastomers have a modulus from about 20 g/mm2 to about 150 g/mm2, and more preferably from about 30 g/mm2 to about 100g/mm2.

If desired, contact lenses prepared from the subject materials may be surface treated to increase wettability using techniques known in the art, for example, plasma surface treatment.

As an illustration of the present invention, several examples are provided below. These examples serve only to further illustrate aspects of the invention and should not be construed as limiting the invention. Example 1 Synthesis of hydroxy-terminated prepolymer is represented by the following synthetic scheme:

To a dried 500 mL round bottom flask equipped with a reflux condenser was added methacryloxypropyl tris (trimethylsiloxy) silane (TRIS, 100 g/0.23 mole), 2- hydroxyethyl methacrylate (HEMA, 9.36 g/0.072 mole) and anhydrous tetrahydrofuran (THF, 100 mL). Oxygen was removεd by bubbling a stream of nitrogεn through thε mixture for 15 minutes. The contents of the flask were then placed under a passive blanket of nitrogen. To the flask was added 2-mercaptoethanol (5.63 g/0.072 mole) and azoisobutylnitrile (AIBN, 0.34 g/0.002 mole) and the mixture was heated for 48 hours at 60°C. Tetrahydrofuran was removed by flash evaporation. The polymer was dissolved in chloroform and washed three times in deiomzed water. The organic layer was dried over anhydrous magnesium sulfate and the resulting polymer was isolated by flash evaporation of the solvent. Analysis by size exclusion chromatography gave number average molecular weight (Mn) 1991, weight average molecular weight (Mw) 2484, with a polydispersity (Pd) of 1.24 (using polystyrene standards).

Examples 2.3

Examples 2 and 3 were prepared using the synthesis of hydroxy-terminated prepolymer as described in Example 1. Table 1 illustrates the formulation and resulting properties.

Table 1 Example TRIS HEMA Moles SH-R-OH Moles Mn Mw Pd (gram) (gram) (gram)

2 100 4.68 0.036 2.82 0.036 2941 3714 1.28

3 100 2.48 0.019 1.49 0.019 4210 5400 1.28

Example 4 Thermoplastic copolvmer elastomer synthesis

To a dried 3-neck round bottom 500-ml flask was added isophorone diisocyanate (IPDI, 3.3192 g/0.0146 mole), neopentyl glycol (NPG, 1.0125 g/0.00972 mole), α,ω- bis(hydroxybutyl) polydimethylsiloxane having a molecular weight of 5,050 (approximately 67 repeating siloxane units) (PDMS, 12.2753 g, 0.00243 mole) and the prepolymer from Example 1 (4.5250 g/0.0243 mole). The molar ratio of IDPI:NPG:PDMS:prepolymer was approximately 3:2:0.5:0.5. To this flask was further added dibutyltin dilaureate (0.0683 g) and dichioromethane (120 ml). The mixture was refluxed under nitrogen. Samples of the reaction product were taken periodically for measurement of 1R spectrum, and the reaction was terminated after about 140 hours when the isocyanate peak (2270 cm" ) disappeared from JR spectrum of the reaction product. The solvent was then stripped under vacuum to give the polymeπc product (Tg = 48°C).

Example 5 Film Samples

The product of Example 4 was dissolved in dichloromethane, and films were obtained by casting the solution over glass plates, followed by evaporating the solvent under vacuum. The mechanical properties of the films were determined on an Instron

Model 4500 using ASTM methods 1708 and 1938. The films had a tensile modulus of

115 g/mm2 and a tear strength of 22 g/mm2.

Example 6 Contact Lens Casting

Ten molds manufactured from polypropylene, having a molding surface to provide an anterior contact lens surface, were charged with 60 mg of a thermoplastic elastomer sample of composition as described in Example 4. A polypropylene mold, having a molding surface to provide a posterior contact lens surface was placed on top of each anterior mold to form a molding cavity therebetween. The two molds were clamped between plates, and then placed between two preheated platens (70°C) and compressed after 2 minutes under pressure. After 10 minutes, pressure was released After the molds were cooled to ambient temperature, the molds were separated by removing the posterior mold and the lenses were peeled from the anterior molds. All lenses were optically clear, and they remained clear when saturated in borate buffered saline.

Example 7 Comparative elastomεr synthesis (elastomer without prepolymer of Example 1)

Following the same procedure as described in Example 4, IPDI (2.1982 g, or 0.00966 mole), NPG (0.5045 g , or 0.00484 mole), dibutyltin dilaurate (0.0813 g) and 30 ml of methylene chloride were added and refluxed for 16 hours. Then, α, ω-bis (4- hydroxybutyl) polydimethylsiloxane (23.9278 g, or 0.00473 mole) and 50 ml of methylene chloride were added and refluxed for another 48 hours. After IR measurement of product showed no presence of isocyanate peak, the reaction was suspended. After stripping off solvent, the product was a viscous clear fluid instead of a solid elastomer.

Example 8 Synthesis of thermoplastic copolvmer elastomer

The procedure described in Example 4 was followed to prepare an elastomer with the same components as described in Example 4, except the ratio of the Example 1 prepolymer and PDMS was changed from 0.5:0.5 to 0.4:0.6. The polymer prepared had Tg of 46°C. The modulus and tear strength of cast films, measured similarly to Example 5, was 62 g/mm2 and 22 g/mm2, respectively.

Example 9 Synthesis of thermoplastic copolvmer elastomer

The procedure of Example 8 was repeated except NPG was replaced with diethylene glycol. The elastomer prepared had a modulus of 25 g/mm2, and had a tear strength of 16 g/mm2.

Example 10 Injection molding of thermoplastic copolvmer elastomer

A polymer sample of Example 8 was dried and injection molded into tensile bars, under the following parameters: feed zone temperature 10°C; nozzle temperature 1 10, 120, 130 or 140°C; mold temperature 20°C; injection pressure 300 bars; injection speed 10 mm/sec. All tensile bars were optically clear.

Many other modifications and variations of the present invention are possible to the skilled practitioner in the field in light of the teachings herein. It is therefore understood that, within the scope of the claims, the present invention can be practiced other than as herein specifically described.

Claims

We claim:
1. A thermoplastic elastomer which is the polymerization product of a mixture comprising:
(A) a hydroxy- or amino-terminated prepolymer prepared by reacting the following components:
(a) at least 60 mole % of an ethylenically unsaturated silicon- containing monomer,
(b) 2.5 to 20 mole % of an ethylenically unsaturated monomer containing a hydroxyl or amino radical,
(c) 2.5 to 20 mole % of a chain transfer agent that provides the prepolymer with hydroxyl- or amino- functional radicals, and
(d) 0 to 20 mole % of an ethylenically unsaturated monomer other than monomers (a), (b) or (c), the mole percent of components (a), (b), (c) and (d) being based on the total molar amount of said components; and
(B) at least one monomer reactive with hydroxyl- or amino-functional radicals of the prepolymer.
2. The thermoplastic elastomer of claim 1, wherein the monomer mixture comprises a silicone containing monomer endcapped with hydroxy or amino radicals.
3. The thermoplastic elastomer of claim 2, wherein the monomer mixture further comprises a diisocyanate.
4. The thermoplastic elastomer of claim 3, wherein the monomer mixture further comprises a diol or glycol having 1 to 40 carbon atoms.
5. The thermoplastic elastomer of claim 4, wherεin the monomer mixture includes an alkylene or oxyalkylene diol having 1 to 10 carbon atoms.
6. The thermoplastic elastomer of claim 3, wherein the monomer mixture includes a dihydroxy- or diamine-terminated silicone-containing monomer.
7. The thermoplastic elastomer of claim 6, wherein the silicone-containing monomer has the formula:
R' R'
I I
HO-R— Si— (O— Si)g-R-OH
R R wheiein each R is independently selected from an alkylene group having 1 to 10 carbon atoms wherein the carbon atoms may include ether, urethane or ureido linkages therebetweεn; each R' is independently selected from monovalent hydrocarbon radicals or halogen substituted monovalent hydrocarbon radicals having 1 to 18 carbon atoms which may include ether linkages therebetween, and a is an integer equal to or greater than 1.
8. The thermoplastic elastomer of claim 7, wherein the diol is neopentyl glycol.
9. The thermoplastic elastomer of claim 8, wherein the diisocyante is isophorone diisocyanate.
10. The thermoplastic elastomer of claim 1 , which is the polymerization product of a mixture that includes a hydroxy- or amino-terminated prepolymer (A), a dihydroxy-terminated silicone-containing monomer, a diisocyanate, and an alkylene or oxyalkylene diol having 1 to 10 carbon atoms.
1 1. The thermoplastic elastomer of claim 1, wherein component (a) of the prepolymer is a compound of Formula (II): wherein:
X denotes -COO-, -CONR4-, -OCOO-, or -OCONR4- where each where R4 is H or lower aikyl; RJ denotes hydrogen or methyl; h is 1 to 10; and each R2 independently denotes a lower alkyl radical, a phenyl radical or a radical of the formula
-Si(R5)3 wherein each R is independently a lower alkyl radical or a phenyl radical.
12. The thermoplastic elastomer of claim 1, wherein component (b) of the prepolymer is selected from the group consisting of hydroxyl-substituted (meth)acrylates, hydroxyl-substituted (meth)acrylamides, amino-substituted (meth)acrylatεs and amino- substituted (meth)acrylamides.
13. The thermoplastic elastomer of claim 12, wherεin component (b) of the prepolymer is at least one hydroxyl-substituted (meth) acrylate selected from the group consisting of 2-hydroxy ethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, glycidyl acrylate, polyethylene glycol methacrylate, and polyethylene glycol acrylate.
14. The thermoplastic elastomer of claim 11, wherεin chain transfer agent (c) of the prepolymer is 2-mercaptoεthanol.
15. The thermoplastic elastomer of claim 1, wherein the prepolymer is based on a copolvmer of tris(trimethylsiloxy) methacryloxy propy silanε, 2-hydroxyethyl methacrylate and mercaptoethanol.
16. A contact lens formed of a thermoplastic elastomer according to claim 1.
17. A contact lens formed of a thermoplastic elastomer according to claim 6.
18. A contact lens formed of a thermoplastic elastomer according to claim 10.
19. A contact lens formed of a thermoplastic elastomer according to claim 15.
20. The contact lens of claim 16, having a water content less than 5 weight percent and a modulus of elasticity of about 20 g mm2 to about 150 g/mm2.
AMENDED CLAIMS
[received by the International Bureau on 26 May 1999 (26.05.99); original claims 1-4,8,10-20 amended; new claims 21 and 22 added; remaining claims unchanged (4 pages)]
1. A thermoplastic elastomer which is the polymerization product of a monomer mixture comprising:
(A) a hydroxy- or amino-terminated prepolymer prepared by reacting the following components:
(a) at least 60 mole % of an ethylenically unsaturated silicon- containing monomer,
(b) 2.5 to 20 mole % of an ethylenically unsaturated monomer containing a hydroxyl or amino radical,
(c) 2.5 to 20 mole % of a chain transfer agent that provides the prepolymer with hydroxyl- or amino- functional radicals, and
(d) 0 to 20 mole % of an ethylenically unsaturated monomer other than monomers (a), (b) or (c), the mole percent of components (a), (b), (c) and (d) being based on the total molar amount of said components; and
(B) at least one monomer reactive with hydroxyl- or amino-functional radicals of the prepolymer.
2. The thermoplastic elastomer of claim 1, wherein component B of the monomer mixture comprises a silicone containing monomer endcapped with hydroxy or amino radicals.
3. The thermoplastic elastomer of claim 2, wherein component B of the monomer mixture further comprises a diisocyanate.
4. The thermoplastic elastomer of claim 3, wherein component B of the monomer mixture further comprises a diol or glycol having 1 to 40 carbon atoms.
5. The thermoplastic elastomer of claim 4, wherein the monomer mixture includes an alkylene or oxyalkylene diol having 1 to 10 carbon atoms.
6. The thermoplastic elastomer of claim 3, wherein the monomer mixture includes a dihydroxy- or diamine-terminated silicone-containing monomer.
7. The thermoplastic elastomer of claim 6, wherein the silicone-containing monomer has the formula:
wherein each R is independently selected from an alkylene group having 1 to 10 carbon atoms wherein the carbon atoms may include ether, urethane or ureido linkages therebetween; each R' is independently selected from monovalent hydrocarbon radicals or halogen substituted monovalent hydrocarbon radicals having 1 to 18 carbon atoms which may include ether linkages therebetween, and a is an integer equal to or greater than 1.
9. The thermoplastic elastomer of claim 22, wherein the diisocyante is isophorone diisocyanate.
10. The thermoplastic elastomer of claim 1, which is the polymerization product of a mixture that includes a hydroxy- or amino-terminated prepolymer (A), a dihydroxy-terminated silicone-containing monomer, a diisocyanate, and an alkylene or oxyalkylene diol having 1 to 10 carbon atoms.
11. The thermoplastic elastomer of claim 1 , wherein component (a) of the prepolymer is a compound of Formula (II): WO 99/33894 PCT/US9-/26I-6-
wherein:
X denotes -COO-, -CONR4-, -OCOO-, or -OCONR4- where each where R4 is H or lower alkyl; R3 denotes hydrogen or methyl; h is 1 to 10; and each R2 independently denotes a lower alkyl radical, a phenyl radical or a radical of the formula
-Si(R5)3 wherein each R5 is independently a lower alkyl radical or a phenyl radical.
12. The thermoplastic elastomer of claim 1, wherein component (b) of the prepolymer is selected from the group consisting of hydroxyl-substituted (meth)acrylates, hydroxyl-substituted (meth)acrylamides, amino-substituted (meth)acrylates and amino- substituted (meth)acrylamides.
13. The thermoplastic elastomer of claim 12, wherein component (b) of the prepolymer is at least one hydroxyl-substituted (meth)acrylate selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, glycidyl acrylate, polyethylene glycol methacrylate, and polyethylene glycol acrylate.
14. The thermoplastic elastomer of claim 11, wherein chain transfer agent (c) of the prepolymer is 2-mercaptoethanol.
15. The thermoplastic elastomer of claim 1 , wherein the prepolymer is based on a copolymer of tris(trimethylsiloxy) methacryloxy propylsilane, 2-hydroxyethyl methacrylate and mercaptoethanol.
-19-
AWIENDED SHEET (ARTICLE 19)
16. A contact lens formed of a thermoplastic elastomer according to claim 1.
17. A contact lens formed of a thermoplastic elastomer according to claim 6.
18. A contact lens formed of a thermoplastic elastomer according to claim 10.
19. A contact lens formed of a thermoplastic elastomer according to claim 15.
20. The contact lens of claim 16, having a water content less than 5 weight percent and a modulus of elasticity of about 20 g/mm2 to about 150 g mm2.
21. The thermoplastic elastomer of claim 7, wherein the monomer mixture further comprises a diol or glycol having 1 to 40 carbon atoms.
22. The thermoplastic elastomer of claim 21 , wherein the diol is neopentyl glycol.
PCT/US1998/026186 1997-12-29 1998-12-10 Silicone-containing prepolymers and low water materials WO1999033894A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US6891197 true 1997-12-29 1997-12-29
US60/068,911 1997-12-29

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE1998606508 DE69806508T2 (en) 1997-12-29 1998-12-10 Silicone-containing prepolymers and materials with low water absorption
JP2000526564A JP2001527141A (en) 1997-12-29 1998-12-10 Silicone containing the prepolymer and low water materials
EP19980963015 EP1042385B1 (en) 1997-12-29 1998-12-10 Silicone-containing prepolymers and low water materials
DE1998606508 DE69806508D1 (en) 1997-12-29 1998-12-10 Silicone-containing prepolymers and materials with low water absorption

Publications (1)

Publication Number Publication Date
WO1999033894A1 true true WO1999033894A1 (en) 1999-07-08

Family

ID=22085505

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/026186 WO1999033894A1 (en) 1997-12-29 1998-12-10 Silicone-containing prepolymers and low water materials

Country Status (6)

Country Link
US (1) US5981669A (en)
EP (1) EP1042385B1 (en)
JP (1) JP2001527141A (en)
DE (2) DE69806508D1 (en)
ES (1) ES2180221T3 (en)
WO (1) WO1999033894A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034347A1 (en) * 1998-12-07 2000-06-15 Bausch & Lomb Incorporated Silicone-containing macromonomers and low water materials
WO2008008752A2 (en) * 2006-07-12 2008-01-17 Novartis Ag Actinically crosslinkable copolymers for manufacturing contact lenses
US8383744B2 (en) 2009-05-22 2013-02-26 Novartis Ag Actinically-crosslinkable siloxane-containing copolymers
US8431624B2 (en) 2009-09-15 2013-04-30 Novartis Ag Prepolymers suitable for making ultra-violet absorbing contact lenses
US8557940B2 (en) 2010-07-30 2013-10-15 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US8642712B2 (en) 2009-05-22 2014-02-04 Novartis Ag Actinically-crosslinkable siloxane-containing copolymers
US8835525B2 (en) 2010-10-06 2014-09-16 Novartis Ag Chain-extended polysiloxane crosslinkers with dangling hydrophilic polymer chains
US8993651B2 (en) 2010-10-06 2015-03-31 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups
US9187601B2 (en) 2010-10-06 2015-11-17 Novartis Ag Water-processable silicone-containing prepolymers and uses thereof

Families Citing this family (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5242876B2 (en) * 2000-03-24 2013-07-24 ノバルティス アーゲー Crosslinking or polymerizable prepolymer
CN1266197C (en) 2000-09-19 2006-07-26 博士伦公司 Method for applying polymeric lens coating
KR20030044027A (en) * 2000-10-24 2003-06-02 보오슈 앤드 롬 인코포레이팃드 Prevention of bacterial attachment to biomaterials by cationic polysaccharides
US6805836B2 (en) 2000-12-15 2004-10-19 Bausch & Lomb Incorporated Prevention of preservative uptake into biomaterials
WO2002049613A3 (en) 2000-12-19 2003-01-16 Bausch & Lomb Method for enhancing integrity of epithelium using retinoic acid
US6702983B2 (en) 2001-05-15 2004-03-09 Bausch & Lomb Incorporated Low ionic strength method and composition for reducing bacterial attachment to biomaterials
US6528464B1 (en) 2001-08-17 2003-03-04 Bausch & Lomb Incorporated Composition and method for inhibiting uptake of biguanide antimicrobials by hydrogels
US7071244B2 (en) * 2002-12-03 2006-07-04 Staar Surgical Company High refractive index and optically clear copoly (carbosilane and siloxane) elastomers
US20060067981A1 (en) * 2004-09-29 2006-03-30 Bausch & Lomb Incorporated Contact lens with improved biocidal activity and related methods and materials
US8197841B2 (en) * 2004-12-22 2012-06-12 Bausch & Lomb Incorporated Polymerizable surfactants and their use as device forming comonomers
US20070123602A1 (en) * 2005-11-29 2007-05-31 Bausch & Lomb Incorporated Use of thermal reversible associations for enhanced polymer interactions
JP4899757B2 (en) * 2006-09-29 2012-03-21 東レ株式会社 Ophthalmic lens
EP2091979A2 (en) 2006-12-13 2009-08-26 Novartis AG Actinically curable silicone hydrogel copolymers and uses thereof
KR101482808B1 (en) * 2007-03-22 2015-01-14 노파르티스 아게 Prepolymers with dangling polysiloxane-containing polymer chains
EP2126614A2 (en) * 2007-03-22 2009-12-02 Novartis Ag Silicone-containing prepolymers with hydrophilic polymeric chains
US8044111B2 (en) 2007-11-30 2011-10-25 Novartis Ag Actinically-crosslinkable silicone-containing block copolymers
CN101896837B (en) * 2007-12-10 2012-05-09 诺瓦提斯公司 Method for making silicone hydrogel contact lenses
US20100069522A1 (en) * 2008-03-17 2010-03-18 Linhardt Jeffrey G Lenses comprising amphiphilic multiblock copolymers
RU2524946C2 (en) * 2008-11-13 2014-08-10 Новартис Аг Polysiloxane copolymers with hydrophilic polymer terminal chains
JP5748224B2 (en) * 2008-11-13 2015-07-15 ノバルティス アーゲー Silicone hydrogel material with a chemically bound wetting agent
CA2868170A1 (en) 2012-03-22 2013-09-26 Anubhav Saxena Organo-modified silicone polymers and hydrogels comprising the same
EP2828692A4 (en) 2012-03-22 2015-10-28 Momentive Performance Mat Inc Hydrophilic macromers and hydrogels comprising the same
US8798332B2 (en) 2012-05-15 2014-08-05 Google Inc. Contact lenses
US9158133B1 (en) 2012-07-26 2015-10-13 Google Inc. Contact lens employing optical signals for power and/or communication
US8857981B2 (en) 2012-07-26 2014-10-14 Google Inc. Facilitation of contact lenses with capacitive sensors
US9523865B2 (en) 2012-07-26 2016-12-20 Verily Life Sciences Llc Contact lenses with hybrid power sources
US9298020B1 (en) 2012-07-26 2016-03-29 Verily Life Sciences Llc Input system
US8919953B1 (en) 2012-08-02 2014-12-30 Google Inc. Actuatable contact lenses
US9696564B1 (en) 2012-08-21 2017-07-04 Verily Life Sciences Llc Contact lens with metal portion and polymer layer having indentations
US9111473B1 (en) 2012-08-24 2015-08-18 Google Inc. Input system
US8820934B1 (en) 2012-09-05 2014-09-02 Google Inc. Passive surface acoustic wave communication
US20140192315A1 (en) 2012-09-07 2014-07-10 Google Inc. In-situ tear sample collection and testing using a contact lens
US9398868B1 (en) 2012-09-11 2016-07-26 Verily Life Sciences Llc Cancellation of a baseline current signal via current subtraction within a linear relaxation oscillator-based current-to-frequency converter circuit
US9326710B1 (en) 2012-09-20 2016-05-03 Verily Life Sciences Llc Contact lenses having sensors with adjustable sensitivity
US8870370B1 (en) 2012-09-24 2014-10-28 Google Inc. Contact lens that facilitates antenna communication via sensor impedance modulation
US8960898B1 (en) 2012-09-24 2015-02-24 Google Inc. Contact lens that restricts incoming light to the eye
US8989834B2 (en) 2012-09-25 2015-03-24 Google Inc. Wearable device
US8979271B2 (en) 2012-09-25 2015-03-17 Google Inc. Facilitation of temperature compensation for contact lens sensors and temperature sensing
US20140088372A1 (en) 2012-09-25 2014-03-27 Google Inc. Information processing method
US8960899B2 (en) 2012-09-26 2015-02-24 Google Inc. Assembling thin silicon chips on a contact lens
US9884180B1 (en) 2012-09-26 2018-02-06 Verily Life Sciences Llc Power transducer for a retinal implant using a contact lens
US8821811B2 (en) 2012-09-26 2014-09-02 Google Inc. In-vitro contact lens testing
US8985763B1 (en) 2012-09-26 2015-03-24 Google Inc. Contact lens having an uneven embedded substrate and method of manufacture
US9063351B1 (en) 2012-09-28 2015-06-23 Google Inc. Input detection system
US8965478B2 (en) 2012-10-12 2015-02-24 Google Inc. Microelectrodes in an ophthalmic electrochemical sensor
US9176332B1 (en) 2012-10-24 2015-11-03 Google Inc. Contact lens and method of manufacture to improve sensor sensitivity
US9757056B1 (en) 2012-10-26 2017-09-12 Verily Life Sciences Llc Over-molding of sensor apparatus in eye-mountable device
US8874182B2 (en) 2013-01-15 2014-10-28 Google Inc. Encapsulated electronics
US9289954B2 (en) 2013-01-17 2016-03-22 Verily Life Sciences Llc Method of ring-shaped structure placement in an eye-mountable device
US9636016B1 (en) 2013-01-25 2017-05-02 Verily Life Sciences Llc Eye-mountable devices and methods for accurately placing a flexible ring containing electronics in eye-mountable devices
US20140209481A1 (en) 2013-01-25 2014-07-31 Google Inc. Standby Biasing Of Electrochemical Sensor To Reduce Sensor Stabilization Time During Measurement
US9161712B2 (en) 2013-03-26 2015-10-20 Google Inc. Systems and methods for encapsulating electronics in a mountable device
US9113829B2 (en) 2013-03-27 2015-08-25 Google Inc. Systems and methods for encapsulating electronics in a mountable device
US20140371560A1 (en) 2013-06-14 2014-12-18 Google Inc. Body-Mountable Devices and Methods for Embedding a Structure in a Body-Mountable Device
US9084561B2 (en) 2013-06-17 2015-07-21 Google Inc. Symmetrically arranged sensor electrodes in an ophthalmic electrochemical sensor
US9948895B1 (en) 2013-06-18 2018-04-17 Verily Life Sciences Llc Fully integrated pinhole camera for eye-mountable imaging system
US9685689B1 (en) 2013-06-27 2017-06-20 Verily Life Sciences Llc Fabrication methods for bio-compatible devices
US9492118B1 (en) 2013-06-28 2016-11-15 Life Sciences Llc Pre-treatment process for electrochemical amperometric sensor
US9307901B1 (en) 2013-06-28 2016-04-12 Verily Life Sciences Llc Methods for leaving a channel in a polymer layer using a cross-linked polymer plug
US9814387B2 (en) 2013-06-28 2017-11-14 Verily Life Sciences, LLC Device identification
US9028772B2 (en) 2013-06-28 2015-05-12 Google Inc. Methods for forming a channel through a polymer layer using one or more photoresist layers
US9572522B2 (en) 2013-12-20 2017-02-21 Verily Life Sciences Llc Tear fluid conductivity sensor
US9654674B1 (en) 2013-12-20 2017-05-16 Verily Life Sciences Llc Image sensor with a plurality of light channels
US9366570B1 (en) 2014-03-10 2016-06-14 Verily Life Sciences Llc Photodiode operable in photoconductive mode and photovoltaic mode
US9184698B1 (en) 2014-03-11 2015-11-10 Google Inc. Reference frequency from ambient light signal
US9789655B1 (en) 2014-03-14 2017-10-17 Verily Life Sciences Llc Methods for mold release of body-mountable devices including microelectronics
US9851472B2 (en) 2015-03-27 2017-12-26 Momentive Performance Materials Inc. Silicone-based hydrophilic copolymer and hydrogel compositions comprising the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0657751A2 (en) * 1993-12-10 1995-06-14 Menicon Co., Ltd. Soft ocular lens material
WO1997022647A1 (en) * 1995-12-21 1997-06-26 E.I. Du Pont De Nemours And Company Coating containing acrylosilane polymer to improve mar and acid etch resistance

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4153641A (en) * 1977-07-25 1979-05-08 Bausch & Lomb Incorporated Polysiloxane composition and contact lens
US5034461A (en) * 1989-06-07 1991-07-23 Bausch & Lomb Incorporated Novel prepolymers useful in biomedical devices
US5010141A (en) * 1989-10-25 1991-04-23 Ciba-Geigy Corporation Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
US5336797A (en) * 1992-12-30 1994-08-09 Bausch & Lomb Incorporated Siloxane macromonomers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0657751A2 (en) * 1993-12-10 1995-06-14 Menicon Co., Ltd. Soft ocular lens material
WO1997022647A1 (en) * 1995-12-21 1997-06-26 E.I. Du Pont De Nemours And Company Coating containing acrylosilane polymer to improve mar and acid etch resistance

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034347A1 (en) * 1998-12-07 2000-06-15 Bausch & Lomb Incorporated Silicone-containing macromonomers and low water materials
WO2008008752A2 (en) * 2006-07-12 2008-01-17 Novartis Ag Actinically crosslinkable copolymers for manufacturing contact lenses
WO2008008752A3 (en) * 2006-07-12 2008-02-28 Novartis Ag Actinically crosslinkable copolymers for manufacturing contact lenses
US9066981B2 (en) 2009-05-22 2015-06-30 Novartis Ag Actinically-crosslinkable siloxane-containing copolymers
US8383744B2 (en) 2009-05-22 2013-02-26 Novartis Ag Actinically-crosslinkable siloxane-containing copolymers
US8642712B2 (en) 2009-05-22 2014-02-04 Novartis Ag Actinically-crosslinkable siloxane-containing copolymers
US8431624B2 (en) 2009-09-15 2013-04-30 Novartis Ag Prepolymers suitable for making ultra-violet absorbing contact lenses
US8557940B2 (en) 2010-07-30 2013-10-15 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US9341744B2 (en) 2010-07-30 2016-05-17 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US8987403B2 (en) 2010-07-30 2015-03-24 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US9052440B2 (en) 2010-10-06 2015-06-09 Novartis Ag Chain-extended polysiloxane crosslinkers with dangling hydrophilic polymer chains
US8993651B2 (en) 2010-10-06 2015-03-31 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups
US9109091B2 (en) 2010-10-06 2015-08-18 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups
US9187601B2 (en) 2010-10-06 2015-11-17 Novartis Ag Water-processable silicone-containing prepolymers and uses thereof
US8835525B2 (en) 2010-10-06 2014-09-16 Novartis Ag Chain-extended polysiloxane crosslinkers with dangling hydrophilic polymer chains
US9921340B2 (en) 2010-10-06 2018-03-20 Novartis Ag Water-processable silicone-containing prepolymers and uses thereof

Also Published As

Publication number Publication date Type
EP1042385A1 (en) 2000-10-11 application
JP2001527141A (en) 2001-12-25 application
EP1042385B1 (en) 2002-07-10 grant
DE69806508D1 (en) 2002-08-14 grant
US5981669A (en) 1999-11-09 grant
ES2180221T3 (en) 2003-02-01 grant
DE69806508T2 (en) 2003-01-16 grant

Similar Documents

Publication Publication Date Title
US4276402A (en) Polysiloxane/acrylic acid/polcyclic esters of methacrylic acid polymer contact lens
US5158717A (en) Method of molding shaped polymeric articles
US5070170A (en) Wettable, rigid gas permeable, substantially non-swellable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units, and use thereof
US6663668B1 (en) Hydratable siloxane comprising porous polymers
US6367929B1 (en) Hydrogel with internal wetting agent
US4543398A (en) Ophthalmic devices fabricated from urethane acrylates of polysiloxane alcohols
US4740533A (en) Wettable, flexible, oxygen permeable, substantially non-swellable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units, and use thereof
US5486579A (en) Wettable silicone hydrogel compositions and methods for their manufacture
US5512609A (en) Reinforced compositions and lens bodies made from same
US5233007A (en) Polysiloxanes, methods of making same and high refractive index silicones made from same
US5449729A (en) UV curable crosslinking agents useful in copolymerization
US5807944A (en) Amphiphilic, segmented copolymer of controlled morphology and ophthalmic devices including contact lenses made therefrom
US4818801A (en) Ophthalmic device comprising a polymer of a telechelic perfluoropolyether
US20080015315A1 (en) Novel Polymers
US5274008A (en) Mold materials for silicone containing lens materials
US5135297A (en) Surface coating of polymer objects
US5962611A (en) Perfluoroalkylether macromer having two polymerizable groups
US5770669A (en) Silcone-containing polymer having oxygen permeability suitable for ophalmic applications
US6891010B2 (en) Silicone hydrogels based on vinyl carbonate endcapped fluorinated side chain polysiloxanes
US5981615A (en) Polymerizable siloxane macromonomers
US5563184A (en) Macromonomers
US5973089A (en) Polymerizable perfluoroalkylether macromer
US5010141A (en) Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
US5070169A (en) Wettable, flexible, oxygen permeable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units and use thereof
US4923906A (en) Rigid, gas-permeable polysiloxane contact lenses

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AU BA BB BG BR CA CN CU CZ EE ES FI GB GE HR HU ID IL IN IS JP KE KG KP KR LC LK LR LT LV MD MG MK MN MW MX NO NZ PL PT RO RU SE SG SI SK SL TJ TR TT UA UZ VN YU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 1998963015

Country of ref document: EP

NENP Non-entry into the national phase in:

Ref country code: KR

ENP Entry into the national phase in:

Ref country code: JP

Ref document number: 2000 526564

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1998963015

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1998963015

Country of ref document: EP